CN103803985B - The preparation method of nanostructured cubic boron nitride-dimond synneusis - Google Patents
The preparation method of nanostructured cubic boron nitride-dimond synneusis Download PDFInfo
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Abstract
本发明涉及一种新型纳米结构立方氮化硼—金刚石聚晶的制备技术。采用六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末为原材料，原材料中金刚石所占质量分数为10%—90%。经净化除杂后，不添加任何粘结剂，装配烧结单元，直接经高温超高压烧结制备纳米结构立方氮化硼—金刚石聚晶。这种纳米结构立方氮化硼—金刚石聚晶，物相分布均匀，立方氮化硼晶粒为纳米尺寸，金刚石晶粒均匀分布在纳米立方氮化硼晶粒中，大面积形成结合紧密、高强度的纳米立方氮化硼—金刚石界面。这使得本发明的高性能纳米结构立方氮化硼—金刚石聚晶的硬度与金刚石单晶硬度相当，热稳定性，硬度，及耐磨性也明显优于含金属粘结剂的金刚石聚晶。
The invention relates to a novel nanostructure cubic boron nitride-diamond polycrystal preparation technology. The mixed powder of hexagonal boron nitride and diamond or the mixed powder of cubic boron nitride and diamond is used as the raw material, and the mass fraction of diamond in the raw material is 10%-90%. After purification and removal of impurities, no binder is added, the sintering unit is assembled, and the nanostructured cubic boron nitride-diamond polycrystal is directly sintered at high temperature and ultra-high pressure. This nano-structured cubic boron nitride-diamond polycrystal has uniform phase distribution, cubic boron nitride grains are nano-sized, and diamond grains are evenly distributed in nano-cubic boron nitride grains. Strength of nanocubic boron nitride-diamond interface. This makes the hardness of the high-performance nanostructured cubic boron nitride-diamond polycrystal of the present invention comparable to that of diamond single crystal, and its thermal stability, hardness, and wear resistance are also significantly better than those of diamond polycrystal containing metal binders.
Description
本发明涉及一种以六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末为原材料，通过净化处理，在高温超高压条件下制备高性能纳米结构立方氮化硼—金刚石聚晶超硬材料的方法，属于无机非金属材料领域。The invention relates to a method of preparing high-performance nanostructured cubic boron nitride-diamond polycrystalline superstructure by using hexagonal boron nitride and diamond mixed powder or cubic boron nitride and diamond mixed powder as raw materials, through purification treatment, under high temperature and ultra-high pressure conditions. The method for hard materials belongs to the field of inorganic non-metallic materials.
技术背景technical background
金刚石与立方氮化硼是目前工业中应用最广泛的两种超硬材料。金刚石是自然界中已知最硬的物质，具有极高的耐磨性、抗压强度、散热速率，金刚石单晶价格昂贵且具有解离面，工业中很多领域使用性价比更高的聚晶金刚石材料来代替金刚石单晶。聚晶金刚石被广泛应用于非铁金属和不含铁合金的切削加工，石油天然气及矿业勘采，木质地板加工等领域。立方氮化硼的硬度约为金刚石的一半，是仅次于金刚石的第二硬材料，但是立方氮化硼拥有比金刚石更高的热稳定性且不易和铁元素发生化学反应，因而可以用来加工铁金属或含铁合金，立方氮化硼单晶价格昂贵且具有解离面，工业中很多领域使用性价比更高的聚晶立方氮化硼材料来代替立方氮化硼单晶。聚晶立方氮化硼由于具有较高的红硬性，较高的耐磨性以及高的热稳定性而被广泛应用于铁金属和含铁合金的切削加工。Diamond and cubic boron nitride are the two most widely used superhard materials in industry. Diamond is the hardest substance known in nature. It has extremely high wear resistance, compressive strength, and heat dissipation rate. Diamond single crystals are expensive and have dissociation surfaces. Polycrystalline diamond materials with higher cost performance are used in many industries. instead of diamond single crystals. Polycrystalline diamond is widely used in the cutting processing of non-ferrous metals and non-ferrous alloys, oil and gas and mining exploration, wood floor processing and other fields. The hardness of cubic boron nitride is about half that of diamond, which is the second hardest material after diamond, but cubic boron nitride has higher thermal stability than diamond and is not easy to chemically react with iron, so it can be used for For processing ferrous metals or ferrous alloys, cubic boron nitride single crystals are expensive and have dissociation surfaces. In many fields of industry, more cost-effective polycrystalline cubic boron nitride materials are used to replace cubic boron nitride single crystals. Polycrystalline cubic boron nitride is widely used in the cutting of ferrous metals and ferrous alloys due to its high red hardness, high wear resistance and high thermal stability.
立方氮化硼—金刚石聚晶材料兼顾了聚晶金刚石与聚晶立方氮化硼的优点，统传的立方氮化硼—金刚石聚晶烧结体是在人造立方氮化硼和金刚石微粉中加入（或不加入直接烧结）Co、Ni、TiC、TiN 等金属粉末均匀混合后，在高压高温下烧结而成的一种超硬复合材料，它在宏观上表现出各向同性和较高的硬度及韧性，在某些方面的应用性能优于聚晶金刚石和聚晶立方氮化硼。但是，传统人造立方氮化硼—金刚石聚晶材料由于粒度较大，很难达到用于超精细切削刀具刃口的平整度和锋利度。另外，传统人造立方氮化硼—金刚石聚晶材料大多含有粘结剂，如：Co、Ni等，严重影响立方氮化硼—金刚石聚晶材料的硬度、耐磨性、热稳定性。Cubic boron nitride-diamond polycrystalline material takes into account the advantages of polycrystalline diamond and polycrystalline cubic boron nitride. The traditional cubic boron nitride-diamond polycrystalline sintered body is added to artificial cubic boron nitride and diamond powder ( (or directly sintered without adding) Co, Ni, TiC, TiN and other metal powders are evenly mixed, and then sintered under high pressure and high temperature. Toughness, in some aspects of the application performance is better than polycrystalline diamond and polycrystalline cubic boron nitride. However, due to the large particle size of the traditional artificial cubic boron nitride-diamond polycrystalline material, it is difficult to achieve the flatness and sharpness of the cutting edge for ultra-fine cutting tools. In addition, most of the traditional artificial cubic boron nitride-diamond polycrystalline materials contain binders, such as Co, Ni, etc., which seriously affect the hardness, wear resistance and thermal stability of cubic boron nitride-diamond polycrystalline materials.
利用六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末为原材料，在高温超高压下制备高性能纳米结构立方氮化硼—金刚石聚晶的报到还未出现。Using hexagonal boron nitride and diamond mixed powder or cubic boron nitride and diamond mixed powder as raw materials to prepare high-performance nanostructured cubic boron nitride-diamond polycrystals under high temperature and ultra-high pressure has not yet appeared.
发明内容Contents of the invention
本发明的目的是为了克服上述传统人造聚晶金刚石、聚晶立方氮化硼、立方氮化硼—金刚石聚晶材料制备技术中的不足，公开了一种以六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末为原材料，原材料中金刚石所占质量分数为10%—90%。通过对原材料净化处理，在高温超高压下制备高性能纳米结构立方氮化硼—金刚石聚晶材料的方法。The purpose of the present invention is to overcome the deficiencies in the above-mentioned traditional artificial polycrystalline diamond, polycrystalline cubic boron nitride, cubic boron nitride-diamond polycrystalline material preparation technology, discloses a kind of hexagonal boron nitride and diamond mixed powder or The mixed powder of cubic boron nitride and diamond is used as the raw material, and the mass fraction of diamond in the raw material is 10%-90%. A method for preparing a high-performance nanostructured cubic boron nitride-diamond polycrystalline material under high temperature and ultrahigh pressure by purifying raw materials.
本发明所述制备的纳米结构立方氮化硼—金刚石聚晶材料的方法按照如下步骤进行：The method for the nanostructured cubic boron nitride-diamond polycrystalline material prepared according to the present invention is carried out according to the following steps:
一、除杂，得到高纯度六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末初始材料。若原料本身很纯，可以不再进行此步骤。除杂的工艺流程为：连续酸溶、粉液分离洗涤、加热烘干三道工序。其中酸的种类，浓度和与原料的比值可根据具体情况适当变动。1. Impurity removal to obtain the initial material of high-purity hexagonal boron nitride and diamond mixed powder or cubic boron nitride and diamond mixed powder. If the raw material itself is very pure, this step can be skipped. The process flow of impurity removal is three processes: continuous acid dissolution, powder-liquid separation and washing, and heating and drying. Wherein the type, concentration and ratio of the acid to the raw material can be appropriately changed according to specific conditions.
a.连续酸溶:（1）将原料置于聚四氟乙烯容器中，加入浓度为20%-40%的氢氟酸，氢氟酸与原料微粉的加入量比值为1-2毫升/克拉 （ml/ct），酸溶时可适当水浴加热（20-100℃）并用搅拌装置连续搅拌，处理时间为72小时。处理完毕后，待微粉沉降完毕，倒去液体，并用去离子水重复稀释至接近中性。（2）将氢氟酸处理后的原料微粉置于玻璃烧杯中，加入浓度为20%-38%的盐酸，或加入浓度为30%-50%的硝酸，酸与原料微粉的加入量比值为1-2毫升/克拉 （ml/ct），酸溶时可适当水浴加热（20-100℃）并用搅拌装置连续搅拌，处理时间为72小时。处理完毕后，待微粉沉降完毕，倒去液体，并用去离子水重复稀释至接近中性。a. Continuous acid dissolution: (1) Put the raw materials in a polytetrafluoroethylene container, add hydrofluoric acid with a concentration of 20%-40%, and the ratio of hydrofluoric acid to raw material powder is 1-2 ml/carat (ml/ct), it can be properly heated in water bath (20-100°C) and stirred continuously with a stirring device when it is acid-soluble, and the treatment time is 72 hours. After the treatment, when the fine powder settles, pour off the liquid and repeat dilution with deionized water until it is close to neutral. (2) Put the raw material powder treated with hydrofluoric acid into a glass beaker, add hydrochloric acid with a concentration of 20%-38%, or add nitric acid with a concentration of 30%-50%, and the ratio of acid to raw material powder is 1-2 milliliters/carat (ml/ct), when acid-soluble, it can be properly heated in a water bath (20-100°C) and continuously stirred with a stirring device, and the treatment time is 72 hours. After the treatment, when the fine powder settles, pour off the liquid and repeat dilution with deionized water until it is close to neutral.
b.粉液分离洗涤：连续酸溶除杂并稀释至中性以后，在烧杯中沉降原料微粉，沉降完毕后倒去液体，留下原料微粉。b. Powder-liquid separation and washing: After continuous acid-dissolving to remove impurities and dilute to neutrality, the raw material powder is settled in a beaker, and the liquid is poured out after the sedimentation is completed, leaving the raw material powder.
c.加热烘干：将烧杯中的留下的原料微粉放入加热炉进行烘干处理，处理温度为70℃，直至烘干。c. Heating and drying: put the remaining raw material powder in the beaker into a heating furnace for drying treatment, and the treatment temperature is 70° C. until drying.
二、真空高温处理：将酸溶除杂后的原料微粉用刚玉坩埚陈放，并用盖子盖住，放入真空炉处理腔。处理时保证真空度优于4x10-3Pa，温度为500-1000℃，处理时间为1-3小时。2. Vacuum high-temperature treatment: put the raw material powder after acid-dissolving and removing impurities in a corundum crucible, cover it with a lid, and put it into the vacuum furnace processing chamber. During processing, ensure that the vacuum degree is better than 4x10 -3 Pa, the temperature is 500-1000°C, and the processing time is 1-3 hours.
三、装配烧结单元：打磨和抛光包裹材料钽箔表面，进行去油、超声波清洗、红外烘干。将处理净化后的原料微粉放入包裹中，预压成型后，放入高压合成装置的样品腔。3. Assembling the sintering unit: Grinding and polishing the surface of the wrapping material tantalum foil, degreasing, ultrasonic cleaning, and infrared drying. Put the processed and purified raw material micropowder into the package, and after pre-pressing, put it into the sample chamber of the high-pressure synthesis device.
四、高温高压烧结：烧结压力为8-20GPa,保压的同时进行加温，烧结温度为1000-2700℃，保温10-30分钟。保温完毕后缓慢降温至300-500℃，开始降压。降压过程中保持温度为300-500℃。4. High-temperature and high-pressure sintering: the sintering pressure is 8-20GPa, heating is carried out while maintaining the pressure, the sintering temperature is 1000-2700°C, and the heat preservation is 10-30 minutes. After the heat preservation is completed, the temperature is slowly lowered to 300-500°C, and the pressure reduction is started. Keep the temperature at 300-500°C during the depressurization process.
五、后续加工：将样品放入30%氢氟酸20ml与40%硝酸20ml混合酸中去除包裹材料钽，采用金刚石磨片打磨样品至光亮。5. Subsequent processing: Put the sample into 20ml of 30% hydrofluoric acid and 20ml of 40% nitric acid to remove the tantalum wrapping material, and use a diamond abrasive to polish the sample until it is bright.
本发明的优点在于：The advantages of the present invention are:
本发明的纳米结构立方氮化硼—金刚石聚晶材料，采用六方氮化硼与金刚石混合粉末或立方氮化硼与金刚石混合粉末为原料，利用高温超高压条件，使原材料中的六方氮化硼相变为纳米结构的立方氮化硼或原材料中的立方氮化硼经高压破碎为纳米晶粒，质量分数为10%—90%的金刚石晶粒作为硬度增强相均匀分布在纳米立方氮化硼晶粒中，大面积形成结合紧密、高强度的纳米立方氮化硼—金刚石界面，最终烧结成纳米结构立方氮化硼—金刚石聚晶。这种高性能聚晶金刚石材料不添加金属粘结剂，而是利用高温超高压条件，使材料物相只含金刚石与立方氮化硼，且通过压力和温度的控制，使原材料中六方氮化硼相变为纳米结构的立方氮化硼或立方氮化硼经高压破碎成的纳米晶粒不再长大。The nanostructured cubic boron nitride-diamond polycrystalline material of the present invention adopts hexagonal boron nitride and diamond mixed powder or cubic boron nitride and diamond mixed powder as raw materials, and utilizes high temperature and ultrahigh pressure conditions to make the hexagonal boron nitride in the raw material The cubic boron nitride in the phase change nanostructure or the cubic boron nitride in the raw material is crushed into nano-grains by high pressure, and the diamond grains with a mass fraction of 10%-90% are uniformly distributed in the nano-cubic boron nitride as a hardness-enhancing phase. In the crystal grains, a large area of tightly combined and high-strength nano-cubic boron nitride-diamond interface is formed, and finally sintered into a nano-structured cubic boron nitride-diamond polycrystal. This high-performance polycrystalline diamond material does not add metal binders, but uses high temperature and ultra-high pressure conditions to make the material phase only contain diamond and cubic boron nitride, and through the control of pressure and temperature, the hexagonal boron nitride in the raw material Cubic boron nitride or cubic boron nitride with boron phase-transformed into nanostructures is crushed under high pressure to form nano-crystal grains that no longer grow up.
本发明所述的高性能纳米结构立方氮化硼—金刚石聚晶的硬度与天然的金刚石单晶硬度相当，热稳定性及切削性能也明显优于含粘结剂的传统人造金刚石聚晶。这种材料不仅可作为普通切削刀具材料，也可作为超高精度切削刀具材料。The hardness of the high-performance nano-structured cubic boron nitride-diamond polycrystal described in the present invention is equivalent to that of natural diamond single crystal, and its thermal stability and cutting performance are also significantly better than traditional artificial diamond polycrystal containing binder. This material can be used not only as a general cutting tool material, but also as an ultra-high precision cutting tool material.
本发明是利用国产铰链式六面顶压机产生的高温超高压条件下制备的高性能纳米结构立方氮化硼—金刚石聚晶。铰链式六面顶压机是目前生产金刚石微粉，烧结传统人造金刚石聚晶的主要设备。本发明可以在现有设备的基础上，大规模制备高性能纳米结构立方氮化硼—金刚石聚晶材料。The invention is a high-performance nano-structured cubic boron nitride-diamond polycrystal prepared under high temperature and ultra-high pressure conditions produced by a domestic hinged six-sided top press. The hinged six-sided top press is currently the main equipment for producing diamond powder and sintering traditional synthetic diamond polycrystals. The invention can prepare large-scale high-performance nanostructure cubic boron nitride-diamond polycrystalline material on the basis of existing equipment.
下面通过附图和具体实施方式对本发明做进一步说明，但并不意味着对本发明保护范围的限制。The present invention will be further described below through the drawings and specific embodiments, but it does not mean to limit the protection scope of the present invention.
附图说明Description of drawings
附图1本发明工艺流程图：Accompanying drawing 1 process flow chart of the present invention:
附图2烧结单元装配图：Attached drawing 2 sintering unit assembly drawing:
附图中各标号标识的对象为：The objects identified by each label in the accompanying drawings are:
1 叶腊石，2白云石，3热电偶，4石墨，5钢碗，6钛片，7样品，8，陶瓷管9，钽杯1 pyrophyllite, 2 dolomite, 3 thermocouple, 4 graphite, 5 steel bowl, 6 titanium sheet, 7 sample, 8, ceramic tube 9, tantalum cup
具体实施方式detailed description
下面通过实施例对本发明进行具体的描述，有必要在此指出的是本实施例只对于本发明进行进一步说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。The present invention is specifically described below through the examples, it is necessary to point out that the present examples only further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to the above-mentioned present invention Some non-essential improvements and adjustments have been made to the content.
实施例1：Example 1:
选用平均粒径为0-2μm的金刚石与平均粒度为0-2μm的六方氮化硼混合粉末，其中金刚石的质量分数为85%，按照图1所示的工艺流程图制备出高性能纳米结构立方氮化硼—金刚石聚晶材料。金刚石与六方氮化硼混合粉末先放入浓度为20%-40%的氢氟酸中处理。氢氟酸与混合微粉的加入量比值为2毫升/克拉 （ml/ct），水浴加热70℃，并连续搅拌，处理72小时。处理完毕后，待微粉沉降完毕，倒去液体，并用去离子水重复稀释至接近中性。将氢氟酸处理后的混合微粉置于浓度为20%-38%的盐酸中，酸与混合微粉的加入量比值为2毫升/克拉 （ml/ct），水浴加热70℃并连续搅拌，处理时间为72小时。处理完毕后，待微粉沉降完毕，倒去液体，并用去离子水重复稀释至接近中性。以上酸溶除杂过程反复进行3-5次后，在烧杯中沉降混合微粉，沉降完毕后倒去液体，留下混合微粉。将留下的混合微粉放入加热炉进行烘干处理，处理温度为70℃，直至烘干。再进行真空高温处理，将除杂后的混合微粉用刚玉坩埚陈放，并用盖子盖住，放入真空炉处理腔。处理真空度为4x10-3Pa，温度为800℃，处理1小时，去除金刚石表面吸附的氧、氮、水蒸气等杂质。Select diamond with an average particle size of 0-2 μm and hexagonal boron nitride powder with an average particle size of 0-2 μm, in which the mass fraction of diamond is 85%, and prepare a high-performance nanostructured cube according to the process flow chart shown in Figure 1. Boron nitride-diamond polycrystalline material. The mixed powder of diamond and hexagonal boron nitride is first put into hydrofluoric acid with a concentration of 20%-40%. The ratio of the amount of hydrofluoric acid to the mixed micropowder is 2 milliliters per carat (ml/ct), heated in a water bath at 70°C, and continuously stirred for 72 hours. After the treatment, when the fine powder settles, pour off the liquid and repeat dilution with deionized water until it is close to neutral. Put the hydrofluoric acid-treated mixed micropowder in hydrochloric acid with a concentration of 20%-38%, the ratio of the acid to the mixed micropowder is 2 milliliters/carat (ml/ct), and heat it in a water bath at 70°C with continuous stirring. The time is 72 hours. After the treatment, when the fine powder settles, pour off the liquid and repeat dilution with deionized water until it is close to neutral. After the above process of acid-dissolution and impurity removal is repeated for 3-5 times, settle the mixed powder in the beaker, pour off the liquid after the sedimentation is completed, and leave the mixed powder. Put the remaining mixed fine powder into a heating furnace for drying treatment, the treatment temperature is 70°C until drying. Then carry out vacuum high-temperature treatment, put the mixed fine powder after removal of impurities in a corundum crucible, cover it with a lid, and put it into the vacuum furnace treatment chamber. The vacuum degree of the treatment is 4x10 -3 Pa, the temperature is 800°C, and the treatment is performed for 1 hour to remove impurities such as oxygen, nitrogen, and water vapor adsorbed on the diamond surface.
按照烧结单元装配图组装烧结单元，如图2所示。先打磨和抛光包裹材料（9）钽箔表面，进行去油、超声波清洗、红外烘干处理。将净化处理后的金刚石与六方氮化硼混合微粉放入包裹中，预压成型，并按照装配图组装烧结单元组。高温高压烧结时，烧结压力为1GPa,烧结温度为1800℃,烧结时间为10分钟。降温降压后，将样品放入30%氢氟酸20ml与40%硝酸20ml混合酸中去除包裹材料钽，采用金刚石磨片打磨样品至光亮。Assemble the sintering unit according to the sintering unit assembly drawing, as shown in Figure 2. Grind and polish the surface of the wrapping material (9) tantalum foil first, then perform degreasing, ultrasonic cleaning, and infrared drying. Put the purified diamond and hexagonal boron nitride mixed micropowder into the package, pre-press, and assemble the sintered unit group according to the assembly drawing. During high temperature and high pressure sintering, the sintering pressure is 1GPa, the sintering temperature is 1800°C, and the sintering time is 10 minutes. After lowering the temperature and pressure, put the sample into a mixed acid of 20ml of 30% hydrofluoric acid and 20ml of 40% nitric acid to remove the wrapping material tantalum, and use a diamond abrasive to polish the sample until it is bright.
采用此工艺制备的高性能纳米结构立方氮化硼—金刚石聚晶材料物相只含金刚石与立方氮化硼，且通过压力和温度的控制，使原材料中六方氮化硼相变为纳米结构的立方氮化硼或立方氮化硼经高压破碎成的纳米晶粒不再长大，此材料具有高硬度和致密度，高的热稳定性，耐磨性和韧性，是一种性能非常优越的新型超硬材料。The high-performance nanostructured cubic boron nitride-diamond polycrystalline material phase prepared by this process only contains diamond and cubic boron nitride, and through the control of pressure and temperature, the phase of hexagonal boron nitride in the raw material is transformed into a nanostructured one. Cubic boron nitride or cubic boron nitride is broken into nano-grains by high pressure and no longer grows. This material has high hardness and density, high thermal stability, wear resistance and toughness, and is a very superior performance. New superhard material.
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